Separation of organic compounds



Sept 25, 1951 w. P. BURTON ETAL 2,568,717

SEPARATION oF ORGANIC COMPOUNDS Filed Oct. 28, 1948 2 Sheets-Sheet l ll r REAcTloN I3 INVENTORS WILLIAM P. BURTON HENRY G. Mc GRATH ATTOR N EYS Patented Sept. 25, 1951 2,588,717 SEPARATION F ORGANIC COMPOUNDS William P. Burton, Orange,-

and Henry G.

McGrath, Elisabeth, N. J., assigner: to The M. W. Kellogg Company, Jersey City, N. J., a

corporation of Delaware Application October 28, 1948, Serial No. 56,928

' s claims. (ci. 26o- 450) This invention relates to the separation of organic compounds and relates more particularly to an improved process for the separationof oxygenated organic compounds from the reaction product obtained in the catalytic hydrogenation o! oxides of carbon at elevated temperatures. Still more particularly, the invention relates to an improved process for the separation and recovery of oxygenated organic compounds from hydrocarbons present in the reaction product obtained in the hydrogenation of oxides of carbon in the prese'nce oi a reducible metal catalyst. wherein these oxygenated compounds comprise alcohols, and acids, and may also comprise esters, aldehydes and ketones, depending upon the conditions of the reaction.

It is, therefore, an object and the process of this invention is directed to provide for an improved process for the separation of the aforementioned oxygenated organic compounds from hydrocarbons present in the reaction product obtained in the catalytic hydrogenation of oxides of carbon, in order to effect eillcient and economical recovery of relatively high yields of such compounds.

Another object of the invention is to provide for an improved process for the separation of the aforementioned oxygenated organic compounds from hydrocarbons present in the -reaction product obtained in the catalytic hydrogenation of oxides of carbon, employing a combination of a minimum number of steps, consistent with eilicient and economical recovery of relatively high yields of such compounds.

Other objects and advantages inherent in the invention will be apparent from the following more detailed disclosure. y

In carrying out the objects of the invention, we employ a novel combination of steps, as more fully hereinafter described. in which the aforementioned synthesis reaction product is condensed and separated into oil. water-product, and uncondensed gas phases which are subsequently treated in a series of interrelated steps from which the aforementioned separation between oxygenated organic compounds and hydrocarbons is obtained. In eiecting such separation between the various compounds present in the reaction product. we are able to obtain: separation of alcohols andacids. either in aqueous solution or in a substantially anhydrous condition; separation of ketones boiling not higher than methyl ethyl ketone; separation of aldehydes boiling not higher than propionaldehyde; and hydrocarbons, substantially water-free, as products of the process.

Figures 1 and 2, taken together, represent a vertical elevation of the apparatus herein em- DlOyed.

The accompanying drawing illustrates diagrammatically one form of the apparatus employed and capable of carrying out one embodiment of the process of the invention. While the invention will be described in detail by reference to the embodiment illustrated in the draw-'- ing, it should be noted that it is not intended that the invention be limited thereto, but is capable of other embodiments which may extend beyond the scope of the apparatus illustrated. Furthermore, the distribution and circulation of liquids and vapors is illustrated in the drawing' by a diagrammatic representation of the apparatus employed. Valves, pumps, compressors, coolers and other mechanical elements necessary to effect the transfer of liquids and vapors and to maintain the conditions of temperature and pressure necessary to carry out the function of the apparatus, are omitted in order to simplify the description. It will be understood, however, that much equipment of this nature is necessary and Will be supplied by those skilled in the art.

Referring to the drawing, a synthesis feed comprising a reaction mixture of hydrogen and an oxide of carbon, at varying mol ratios, such as 2:1, is supplied through line I0 and transferred through this line to a synthesis reaction vessel, represented in the drawing by reactor II. In reactor I I, the reaction -mixture is contacted with a hydrogenation catalyst, such as a reduced iron or cobalt catalyst, at temperatures varying between about 300 F. and about '700 F. and at pressures varying between about atmospheric pressure and about 500 pounds per square inch, and is carried out according to conventional fixed-bed or fluid-bed operations. The resulting reaction product obtained from reactor II is withdrawn through line I2. This product is in the vapor form substantially as it comes from the reactor within the aforementioned temperature range, containing water, methane and higher hydrocarbons, and oxygenated organic compounds comprising Cz and higher acids, methanol and' higher alcohols and which may also comprise aldehydes, ketones, esters, and depending upon the condition of the reaction, is rst cooled to condense substantially large quantities of normally liquid components. Conveniently, condensation may be eil'ected in a plurality of cooling stages which are represented diagrammatically in the drawing by cooler I3 vwith which line I2 connects. From cooler Il the resulting mixture of condensate and uncondensed gases passes BEST AVAILABLE COPY assi-mir through line I l to separator I5. ln the latter,

i rre withdrawn through line I6 and the condensan separates as a lower aqueous phase and an u per oil phase. Both phases thus obtained contain oxygenated organic compounds; those of lower molecular weight tending to remain in the aqueous phase, while those of higher molecular weight tend to remain in the oil phase.

f s phase is drawn oil' from the bottom tsr I5 through line I1 and the oil phase i n orf at an intermediate point through line itD lt should be noted that apparatus embodying more than one separation stage may be employed, if desired; for example, primary and secondary separation stages may be introduced, operating successively and respectively at temperatures of about 150 F. and about 100 F.

The gases separated in separator I5 are passed through line I6 to a low point in a, suitable scrubbing vessel I9. In this gas scrubber, the gases are intimately contacted with an aqueous solution of relatively light organic acids, obtained from the source hereinafter described, in order to extract the oxygenated compounds present. For this purpose, this aqueous solution is introduced into scrubber I9 at an upper point through line 20. The scrubbed gaseous eiliuent, essentially free of oxygenated organic compounds and comprising a mixture of the relatively lighter hydrocarbons, is withdrawn overhead through line 2|. This mixture is next treated with alkali in order to effect neutralization of traces of organic acids that may be present. For this purpose, the mixture of hydrocarbons in line 2| is next transferred through this line to a caustic treater 22, in which it is intimately mixed with alkali in a suitable amount through line 23. After the components of the mixtire are maintained in intimate contact for a time suillcient to effect the desired neutralization of traces of organic acids present in the aforementioned hydrocarbon mixture, the treated mixture is seaparated in the form of an upper gaseous hydrocarbon phase. substantially acid-free and a lower aqueous phase comprising alkali salts of organic acids. The aforementioned upper phase is withdrawn from treater 22 through line 24 for further use or treatment outside the scope of the present process. The lower aqueous phase from treater 22 is withdrawn through line 25, f and may be subjected to conventional methods of treatment, known to those skilled in the art, for the conversion of. the alkali salts to their corresponding free organic acids.

The remaining mixture of oxygenated organic compounds in scrubber I9, comprising methanol and higher alcohols, C2 and higher aldehydes, ketones, acids and esters is transferred through line 26 and combined with the water-product liquid phase withdrawn from separator I5 through line I1, for further treatment in the process hereinafter described. The oil phase separated in separator I5 is transferred through line I8 to a low point in an oil scrubber 2l, in which the oil is contacted intimately with water to absorb in the water the oxygenated compounds which are diolved in the oil and which are relatively more soluble in water. such as the relatively low-boiling alcohols, ketones, aldehydes and acids. Water employed for this purpose is introduced to the upper part of scrubber 2l through line 28. 'I'he scrubbing water containing dissolved oxygenated compounds is withdrawn from the bottom oi' oil scrubber 21 through line 2l. and is transferred through line 20 and combined with the water-product withdraws f mn separator |5 through line Il, for furthe eax ment in the process hereinafter describe i The scrubbed oil is withdrawn overhi a s rf. scrubber 21 through line 30. This oil, v `m ing essentially a mixture o! organic aci hols, esters, aldehydes, ketones and h mi' bons, is transferred through line 30 t` 1 o point in an extraction tower 3|. In tow oil introduced through line 30 is sub; i intimate countercurrent contact with a t u il. light alcohol as a treating agent, such a i. nol or ethanol, which is introduced into `l at an upper point through line 32. Thr im i?, treating agent and the oil are contacted i.. 3| under conditions eifective to absorb treating agent substantially all of the ox may compounds contained in the oil and thi f I separation of these oxygenated compou 'om hydrocarbons present. As a result of 'uw oregoing treatment, a lower aqueous alcotif; layer and an upper hydrocarbon or oil layer are formed in tower 3|. Inasmuch as anhydrous light alcohols exhibit high soiubllities for hydrocarbons as well as for oxygenated compounds, dilution of such alcohols will eflect an improvement in tue selectivity of extraction, so that absorption of hydrocarbons in the alcohol treating agen; is substantially prevented. To obtain such dilutior i. water is introduced into tower 3| at an upper point above the alcohol inlet through line 33. The use of water in the manner described is effective not only for the purpose of alcohol dilution, but its introduction at an upper point in tower 3| accomplishes the result of washing thi;I

upper hydrocarbon or oil layer free of the added alcohol treating agent.

Aqueous methanol used as a treating agent in the present embodiment is not, however. completely selective in effecting total extraction of oxygenated organic compounds from hydrocarbons present in tower 3|. Hence, the liquid flowing down tower 3| will contain some hydrocarbons in solution in addition to oxygenated organic compounds. These hydrocarbons may comprise a mixture of proportionately small quantities of all the hydrocarbons present in the oil stream entering tower 3| through line 30. and would render separation of pure oxygenated compounds highly dimcult. A relatively light hydrocarbon stream functioning as a wash-oil is therefore introduced at a point near the bottom of tower 3| through line 34. This hydrocarbon stream effects the washing of the lower aqueous methanol layer in tower 3|, free of hydrocarbons contained therein, leaving the methanol layer saturated with the wash-oil. It is desirable that this wash-oil be of such composition that there are no components present in a substantial amount that are heavier than the highest boiling hydrocarbon which forms an azeotrope with the alcohol treating agent. The boiling point of the wash-oil selected must therefore be substantially within or below the boiling range of the oxygenated compounds that are to be separated. Hence, we may use such wash-oils as butane. pentane, hexane, or heptane or mixtures thereof. Following the above-mentioned wash-oil treatment, there is present in tower 3| an upper hydrocarbon or oil layer containing substantially all the hydrocarbons that were present in the oil stream entering tower 3| through line 3l. and a portion of the wash-oil; and there is also present a lower aqueous methanol layer saturated with wash-oil and containing extracted oxygen- B ated compounds. The upper hydrocarbon or oil layer is withdrawn overhead as a raffinate from tower Ji through line IB. while the lower aqueous methanol layer is withdrawn as an extract through line It. The aforementioned mixture of. hydrocarbons withdrawn as an overhead railinats through line 35 is next treated with alkali in order to effect neutralization of traces of organic acids that may be present. For this purpose. the mixture of hydrocarbons is next transferred through line 35 to a caustic treater 31, in which it is intimately mixed with alkali in a suitable amount introduced through line 3l. After the components of the mixture are maintained in intimate contact for a time suiiicient to eil'ect the desired neutralizationy of traces of organic acids present in the aforementioned hydrocarbon mixture, the treated mixture is permitted to settle in order to form an upper hydrocarbon phase, substantially acid-free, and a lower aqueous phase comprising alkali salts of organic acids. The aforementioned upperv phase is withdrawn from treater 31 through line 39 for further use or treatment outside the scope of the present process. The lower aqueous phase from treater II is withdrawn through line 40, and may be subjected to conventional methods of treatment known to those skilled in the art, for the conversion of the alkali salts to their corresponding free organic acids.

The lower aqueous methanol layer from tower Il, saturated with wash-oil and containing oxygenated compounds, is transferred through line Il to a fractionation tower Il. Tower Il, functioning as a methanol stripper, is operated under conditions effective to separate the aqueous methanol layer, introduced from tower 3| through line Il, into an overhead alcohol fraction comprising essentially methanol and hydrocarbons which is withdrawn through line 32, and a lower fraction normally consisting of two phases; one phase comprising oxygenated compounds and the other phase comprising water containing some dissolved oxygenated compounds. 'Ihese combined phases are withdrawn as bottoms through line 42. The overhead alcohol fraction from tower 4l is withdrawn through line 32 as a vapor, and is cooled to liquefy methanol and hydrocarbon components. The mixture of methanol and hydrocarbons thus liquefied is transferred through line 32 into tower 3i for repeated use as the methanul treating agent in the process herelnbefore described. Make-up methanol is introduced through line I3 via line 32 with which line 43 connects. Bottoms from tower 4i, comprising an aqueous mixture of dissolved oxygenated com pounds, namely, relatively heavy alcohols, aldehydes, ketones, acids and relatively smaller proportions of esters, are next transferred through line 42 to a hydrogenation reactor 4I. Reactor I4 is provided for effecting catalytic hydrogenation, by conventional methods, of aldehydes and ketones present in the aforementioned mixture to their corresponding alcohols. Hydrogen employed in reactor M is introduced through line 45. Following the conversion of aldehydes and ketones into alcohols in hydrogenation reactor M the product of the reaction is withdrawn as bottoms through line I6. Bottoms thus obtained are cooled and transferred through line 46 to a separator I1. In separator 41, separation is obtained between the aqueous mixture of alcohols, acidsl and esters which is withdrawn as bottoms through line 48, and free hydrogen which is re- 6 eycledtoreactor Il throughlineltvialine. with which line 4l connects.

In order to obtain substantially complete separation of alcohols from organic acids and esters present in the aqueous mixture in line Il, this mixture is next contacted with an alkali or an aqueous solution of an alkali to convert the organic acids to an aqueous solution of their corresponding alkali salts and to saponify esters. For this purpose, the mixture in line Il is next transferred through this line to a caustic treater Il in which it is intimately mixed with alkali, such as sodium or potassium hydroxide, in a suitable amount introduced through line l I 'Ihe resulting mixture from treater il, comprising an aqueous solution of alcohols and alkali salts of organic acids'is withdrawn through line l2,

We have found that if the above-mentioned aqueous mixture of alcohols and alkali salts of organic acids is subjected to phase separation, substantially complete separation between alcohols and alkali salts cannot be obtained by reason of the mutual solubility of the components of these phases. We have also' found that simple distillation of the alcohols from alkali salts is not feasible, inasmuch as the boiling point oi.' some of the alcohol components Present are too high to permit distillation without decomposition at atmospheric pressure. To overcome the resulting disadvantages when employing the abovementioned procedures, we next subject the aforementioned mixture to reduced pressure to evapcrate substantially all of the alcohols present in order to leave dry alkali salts as a residue, as more fully explained in our prior and co-pending application Serial No. 776,366, led September 26, 1947. For this purpose, the mixture in line .52 is next preheated by any suitable conventional means (not shown in the drawing) to raise the temperature of the mixture to a temperature approximately at which evaporation will take place, but below the point of decomposition of any of the components of the mixture. The heated mixture is next transferred through line I! to an evaporation chamber, represented in the drawing by vacuum dryer 53. In dryer 53 the mixture is next subjected to evaporation or flashing at a reduced pressure, below atmospheric pressure such as a combined vapor pressure of the solution and alcohols of not more than 25 mm. of mercury as disclosed in the aforementioned application Serial No. 776,366. At this point, it should be noted that the aforementioned operation may be carried out batch-wise or as a continuous operation. In continuous operations, the feed in line 52 may be fed into dryer 83 as a spray, the resulting alcohol vapors being taken overhead and the remaining dry salts withdrawn from the bottom through a vacuum seal, such as a lock hopper. When it is desired to -carry out the foregoing operation step as a continuous process, this may also be eiected by the use of an enclosed drum dryer. In the latter method, the alcohols are evaporated from the hot surface .of the drums and the remaining salt .cake continuously scraped from the rotating drum and vdischarged through a vacuum seal. y The separated alcohols in dryer 53 are withdrawn overhead as vapors through line N.

These vapors are next condensed and transferred through line to a distillation tower` il.

-Tower 55 is heated under proper operating conditions of temperature and pressure to distill overhead the relatively low-boiling alcohols as an aqueous mixture, which are withdrawn through assaut' line It and which may be transferred to suitable conventional fractionation apparatus for the separation of individual components. Bottoms from tower il. comprising relatively heavier alcohols. substantially water-free. are withdrawn through line I1 and may also be transferred to suitable conventional fractionation apparatus for the scparation of individual components.

The separated dry alkali salts of organic acids are withdrawn as bottoms from tower 53 through line Il. 'I'hese salts are transferred by gravity through line |50 to a separator 59. In order to eifect regeneration of the organic acids in line Il from their salts, an inorganic acid is introduced into this line through line 60. 'I'he inorganic acid thus introduced into line 5l through line 0l may be a high-boiling inorganic acid having a boiling point higher than that of water, such as sulfuric acid. or an inorganic acid which forms a maximum boiling azeotrope with water, such as hydrochloric acid.

The resulting aqueous mixture in separator 59, comprising free organic acids and alkali salts of the introduced inorganic acid, will separate into two phases. By reason of their insolubility in the water solution, the relatively heavier organic acids will be obtained as an upper acid-rich phase in separator I9 and are withdrawn overhead through line 6I. The lower water-rich phase which is formed in separator 59. comprising inorganic salts and relatively lighter water-soluble organic acids, is withdrawn as bottoms through line I2, for further treatment in the process hereinaftcr described.

The upper acid-rich phase withdrawn from separator Il through line 6|, comprising the aforementioned relatively heavier organic acids, may also contain some of the relatively lighter acids and water in minor proportions. This mixture is, therefore. next transferred through line Il to a distillation tower 83. Tower 83 is operated under proper conditions of temperature and pressure effective to distill overhead an aqueous mixture of the relatively light acids which is withdrawn as a relatively low-boiling mixture through line 6I for further treatment in the process hereinafter described, while the relatively heavier acids will separate out as a lower relatively high-boiling fraction, which is withdrawn through line 85, in a substantially anhydrous condition and may be transferred to any conventional acid fractionation system in whichindividual acids may be recovered for further use outside the scope of the present process.

At this point it should be noted that the aforementioned bottoms from tower 4l (comprising an aqueous mixture of dissolved oxygenated compounds, nameLv, relatively smaller proportions of esters), may be subjecled to a preliminary separation stage, if so desired, prior to the aforementioned hydrogenation in reactor u. For this purpose, the mixture in line 42 may be transferred through line 66 to a settler B1 to effect separation at this point between oil-soluble and water-soluble chemicals present in the mixture. Such separation may be desirable, inasmuch as the absence of water in reactor u will facilitate the ease with which hydrogenation of aldehydes and ketones to alcohols can .be effected. In settler 81 there are thus obtained an upper oil layer and a lower aqueous layer, each layer containing a portion of each class of compounds present in the mixture in line 42. The upper oil layer from settler 61 is next transferred to reactor M through line il via line l2 for hydrogenation of aldehydes and ketones to alcohols. as previously described. 'I'he lower aqueous layer from settler Il is withdrawn through line Il. combining with the bottoms from oil scrubber 2l in line 2l, and the combined stream transferred through line 2l into line 28 where it is further combi'ncd with the water product liquid phase in line I As indicated above, the streams combined in line Il, comprise an aqueous mixture of methanol and higher alcohols. Cz and higher aldehydes, ketones, acids and esters. This aqueous mixture is next transferred through line Il to a distillation tower ll which functions as an aicohol stripper. In tower 1I. the mixture of oxygenated compounds is heated under properI operating conditions of temperature and prsure effective to distill overhead alcohols. aldehydes. ketones and esters which are withdrawn through line li. Bottoms obtained from tower 1I, comprising an aqueous solution of relatively light organic acids. are withdrawn through line I2 for further treatment in the process hereinafter described. Aspreviously indicated, the gases in scrubber Il are intimately contacted with an aqueous solution of relatively light organic acids to extract oxygenated compounds present. It is, therefore, possible to transfer the bottoms from tower Il (comprising an aqueous mixture of relatively light organic acids) withdrawn through line l2, directly into scrubber I.. via line Il with which line 'l2 connects.

The overhead from tower l0 comprising a mixture of relatively light alcohols. aldehydes. ketones and esters is transferred through line 'Il to a distillation tower ll. In tower ll the mixture is heated under proper operating conditions of temperature and pressure elective to distili overhead the lowest boiling components of the mixture which may be acetaldehyde, propionaldchyde. methanol, methyl ethyl ketone and acetone which are withdrawn through line 14. Bottoms from tower ll. comprising relatively light alcohols and ketones, are withdrawn through line 1l. These bottoms may contain alcohols having up to eight or more carbon atoms per molecule. aldehydes boiling higher than propionaldehyde, and may contain in addition, ketones, esters.

traces of organic acids and water. 'I'he overhead from tower 13. may next be transferred through line 'Il to a distillation tower 1i. Tower 'II is heated under conditions of temperature and pressure effective to distill overhead the lowest boiling components of the mixture which boil not higher than propionaldehyde. These components may be withdrawn through line ll for further use or treatment outside the scope of the present process. Bottoms from tower ll, comprising those oxygenated compounds boiling not higher than the boiling point of methyl ethyl ketone (and which normally include methanol and acetone) are withdrawn through line Il for further use or treatment also outside the scope of the present process. It should be noted at this point that where so desired. methanol present in line I2. as Previously indicated, may be transferred from this line through line 'Il and combined with the overhead'from tower 'Il in line 1I, with which line 1l connects, for further separation in the process hereinbefore described.

As stated above, the overhead from tower Il comprises the lowest boiling components of the mixture introduced into this tower. through line Il. which boil not higher than prop.

This overhead may next be withdrawn through line 11, as stated above, or combined in line 11 with the bottoms from tower 18 through line 1I, with which line 11 connects. 'I'hus there is obtained in line 11, a mixture which may comprise alcohols having up to eight or more carbon atoms' per molecule, aldehydes, ketones, esters, traces of organic acids and water. This mixture is next transferred through line 80 to a hydrogenation reactor 8|. Reactor 8| is provided for effecting catalytic hydrogenation, by conventional methods, oi' aldehydes and ketones present in the aforementioned mixture to their corresponding alcohols. Hydrogen employed in reactor 8| is introduced through line 82. Following the conversion of aldehydes and ketones into alcohols in reactor Il, the product of the reaction is withdrawn as bottoms through line 89. Bottoms thus obtained are cooled and transferred through line 89 to a seperator 84. In separator Il, separation is obtained between the aqueous mixture of alcohols, acids and esters which is withdrawn as bottoms through line 85, and free hydrogen which is recycled to reactor 8| through line 80, via line 82, with which line 88 connects.

In order to obtain substantially complete separation of alcohols from organic acids and esters present in the aqueous mixture in line 85, this mixture is next 4contacted with an alkali or an aqueous solution of an alkali, such as sodium hydroxide or potassium hydroxide, to convert the organic acids to an aqueous solution' of their corresponding alkali salts and to saponify esters. For this purpose, the mixture in line 85 is next transferred through this line to a caustic treater 81, in which it is intimately mixed with alkali in a suitable amount introduced through line 88. The resulting mixture from treater 01, comprising an aqueous solution of alcohols and alkali salts of organic acids, is withdrawn through line 89.

I'he aforementioned aqueous solution of alcohols and alkali salts of organic acids in line 89, may contain relatively small quantities of hydrocarbons as impurities. 'I'hese hydrocarbons present in the above mixture, must be removed in order to effect the subsequent recovery of pure pentane but requiring the stripping of lighter hydrocarbons out of the hexane as well as the stripping of hexane from the heavier hydrocarbons. The choice of a suitable hydrocarbon will be influenced by its solubility and by its boiling point or the boiling points of its azeotropes with light alcohols.

To effect the removal of such contaminating hydrocarbons, the mixture from caustic treater 81 is transferred through line 89 to an extraction tower 90. In tower 90 the mixture introduced vthrough line 89, is subjected to intimate countercurrent contact with pentane or other selected suitable hydrocarbon treating agent, which is introduced at a low point into tower 90 through line 9|. The treating agent and the aforementioned alcohol mixture, containing hydrocarbons, are contacted in tower 90 under conditions eifective to absorb in the treating agent, the hydrocarbone present. In order to prevent loss of a portion of the resulting alcohol phase produced in tower 90 in the treating agent extract, water may be introduced at an upper point into tower 90 through line 92 to reabsorb the alcohol from the extract thus obtained. 'I'he bottoms thus produced in tower 90, comprising an aqueous mixture of alcohols having up to eight or more carbon atoms per molecule, alkali salts of heavy organic acids, excess alkali and a portion of the pentane treating agent, are withdrawn through line 93 for further treatment in the process hereinafter described. The overhead from tower 9|, comprising the bulk of the pentane treating agent and higher hydrocarbons, together with small quantities of alcohols, is withdrawn through line 94 for further use or treatment outside the scope of the present process. The bottoms from tower 90 are next transferred through line 93 to a distillation tower 95, to effect the removal of the pentane treating agent from the alcohol stream. In tower 95, the mixture is heated under proper conditions of temperature and pressure, to distill overhead pentane which is withdrawn through line 9| for further use in tower 90 in alcohols. It has been found that the hydrocarbons tend to concentrate as their homogenous alcohols azeotropes in 'the distillation cuts taken between the various alcohols. In such aqueous alcohol solutions, contaminating hydrocarbons can be removed efficiently and economically by means of one or more hydrocarbons which are themselves readily removable. In principal, the process may be considered as one of dilution rather than extraction, in that the undesirable hydrocarbons are replaced by one or more of the aforementioned hydrocarbons which may be readily eliminated.

Such a hydrocarbon may be n-pentane, which is highly suitable in over-all use as applied to the aforementioned process and as evidenced by experimental laboratory data. It should be noted, that the operation is not restricted to the sole use of pentane for the purpose indicated, but that other lighter or heavier hydrocarbons may also be successfully employed, such as butane or heptane. Butane has the advantage of not being known to form an azeotrope with methanol, although it has a high solubility in aqueous alcohol solutions. On the other hand, it may be desirable to use heavier hydrocarbons as a solvent such as hexane, the latter being less soluble than the process hereinbefore described. Make-up pentane is introduced into line 9| through line 96, with which line 9| connects.

As a result of the process, hereinbefore described, bottoms from tower 95 withdrawn through line 91, comprise an aqueous mixture of alcohols, salts of organic acids and ,excess alkali. This aqueous mixture is next transferred through line 91 to a distillation tower 98. Tower 98 is operated under proper conditions of temperature and pressure effective to distill overhead an aqueous solution of relatively light alcohols which are withdrawn through line 99, and which may be transferred to any conventional fractionation apparatus, known to those skilled in the art. for the separation of individual alcohol components. Bottoms from tower 98, comprising an aqueous mixture of salts of organic acids and excess alkali are withdrawn through line |00.

In accordance with the process of the invention, the aqueous mixture in line |00 is next subjected to further treatment in order to release organic acids present from their salts. This mixture is, therefore, contacted in line |00 with a high-boiling inorganic acid having a boiling point higher than that of water, such as sulfuric acid, or an inorganic acid which forms a maximum boiling azeotrope with water, such as hydrochloric acid. The inorganic acid thus employed is introduced into line |00 through line |0|, with which line |00 connects. The resulting solution in line comprising inorganic salts.V excess quantities of the introduced inorganic acid, released organic acids. and excess water, is transferred through line |0| and combined with the aforementioned lower `water-rich phase from separator I0 Ain line 02. comprising inorganic salts and relatively lighter water-soluble organic acids.

As hereinbefore described, the bottoms withdrawn from tower through line 12 comprise an aqueous mixture of relatively light organic acids. These bottoms may next be combined in this line with the aforementioned aqueous mixture of relatively light organic acids. inorganic salts and excess quantities of the introduced inorganic acid present in line 02, for further treatment. Accordingly, the combined streamin line 12 is next transferred to an extraction tower |02. In tower |02 the stream introduced through line 12 is subjected to intimate countercurrent contact with an omen-containing solvent treating agent as an acid extractor, such as ethyl acetate, ethyl ether, isopropyl ether, or ketones such as methyl propyl'ketone, either singly or in admixture. which is introduced into tower |02 through line |00. The treating agent and the aqueous stream of organic acids are contacted in tower |02 under conditions effective to absorb in the treating agent a large proportion of the acids contained in the aqueous stream of organic acids passing through line 12. The extract thus produced comprises an acid-richY mixture containing organic acids, excess quantities oi' the solvent treating agent and proportionately small quantities of water. and is withdrawn overhead from tower |02 through line |04. Bottoms from tower |02, comprising a r'alna'te containing a portion of the solvent treating agent and proportionately large quantities of water, are withdrawn through line |00.

The extract from tower |02, comprising an acid-rich mixture containing organic acids, excess quantities of the solvent treating agent and proportionately small quantities of water, is withdrawn overhead through line |04 and transferred through this line to a dehydration tower |00, which functions as a stripper for the solvent treating agent. Tower |00 is heated under conditions of temperature and pressure effective to distill overhead a mixture containing substantially all oi' the solvent treating agent and water present in line |01, which is withdrawn through line |03, and is transferred through this line for fm'ther use as the solvent in tower |02 in the process described above. Bottoms from tower |00, comprising substantially'waterfree Ca and heavier organic acids, solvent-free, are withdrawn through line |01, and may be transferred to any conventional acid fractionation system in 'which individual acids may be recovered for further use outside the scope of the present process.

As hereinbefore described, the ramnate from tower |02 contains a portion of the solvent treating 'agent and proportionately large quantities of water, inorganic salts and excess quantities of the introduced inorganic acid. This raffinate is next transferred through line |00 to a distillation tower |00 tower |00 is heated under conditions of temperature and pressure eifective to distill overhead water-azeotropes of the solvent treating agent which are withdrawn through line |00.

' Bottoms from tower |00. comprising excess water,

inorganic salts and any excess quantities of the introduced inorganic acid that may be present are withdrawn through line ||0. The waterausm-r i2 azeotropes of the solvent treating agent which are withdrawn overhead from tower |00 through line illaretransferredintoaseparator In separator ||I separation is effected between an upper layer, comprising the solvent treating agent, and a lower water-layer which is withdrawnasbottoms throughline ||2 andistransferred into tower |00 for further treatment in the process described above. The upper layer from separator comprising the solvent treating agent, is withdrawn through line ||3 and transferred via line |03, with which line ||I connects, for further use in tower |02 as described above. *Make-up solvent is introduced into line |03 through line lil with which line |00 connects. At this point, it should be noted that, as previously described, the overhead withdrawn from tower nv through line 04 comprises an aqueous mixture of relatively light organic acids.

Accordingly. this mixture may next be transferred through line 04 into line |00 for dehydration in tower |06 as described above.

In some instances, the mixture of substantially water-free organic acids withdrawn from tower |00 through line |01. may contain very small amounts of alcohols and carbonyls as impurities. If so desired, it is possible to remove these impurities by methods such as polymerization. Accordingly, the mixture in line |01 may be transferred through line Il, with which line |01 connects, to an acid treater Ill. In treater ||0 the mixture is contacted with a polymerixing agent such as an inorganic acid which may be sulfuric acid, which is introduced through line withdrawn through line |20, and polymerised allcohols and carbonyls which are withdrawn as a ||1 in an amount sumcient to polymeriae any of the aforementioned impurities present, in the form of a sludge. The resulting mixture from treater ||0 is next transferred through line ||0 to an evaporation tower, represented in the drawingbyfiashtower Il. Intower lllthemixttn'e is subjected to flashing to effect separation between anhydrous light organic acids which are residue through line |2I. The mixture of anhydrous acids withdrawn through line |20 may contain some quantities of sulfur as contami-- nants. This mixture is next transferred through line |20 to a stripping acne. represented in the drawing by stripper |22. where it is air-blown with air being introduced ata low point in stripper |22 through line |21. As a result of the treatment in stripper |22, sulfur present in the acid mixture introduced through line |20 is withdrawn overhead in the form of sulfur dioxide through line |24; while substantialLv water-free light organic acids, free of any of the aforementioned contaminants, are withdrawn through line |25, via line |01 with which line |20 connects. for further fractionation of individual acid components.

As previously stated, the novelty of the present invention resides in a combination of steps in which the aforementioned synthesis reaction product is condensed and separated into oil, water-product and gas phases whichintumaresubsequcntlytreatedinaserin of interrelated steps from which separation between the aforementioned oxygenated organic compounds and hydrocarbons is obtained. Among the most important of these interrelated steps are:

(I) Separation of the reaction product into three 'phases (namely. an uncondensed gas phase, oil-product and water-product liquid ascanv y phases); water scrubbing the oil-product liquid phase to obtain alower water-layer comprising dissolved oxygenated compounds and hydrocarbons; separating these layers; subjecting the upperoil-layer to extraction treatment with an aqueous solution of a water-soluble alcohol vto obtain a ramnate comprising a maior portion of hydrocarbons and a minor portion of oxygenated organic compounds present in the upper oil-layer, and an extract comprising a major portion of oxygenated compounds and a minor portion of hydrocarbons present in this layer; extracting the extract with a hydrocarbon wash-oil to absorb hydrocarbons present; neutralizing the railinate to obtain an upper phase comprising acid-free hydrocarbons and a lower phase comprising an aqueous solution of alkali salts; combining the lower waterlayer obtained from water-scrubbing of the oilproduct liquid phase with water-product liquid phase; fractionating the combined streams into a relatively low-boiling fraction comprising nonacid oxygenated compounds and a minor portion of organic acid present in the water-product liquid phase, and a relatively high-boiling fraction comprising a major portion of organic acids present in the water-product liquid phase; scrubbing the uncondensed gas phase with the aforementioned relatively high-boiling fraction to obtain a scrubbed gaseous eiliuent comprising a major portion of hydrocarbons and a minor portion of organic acids present in the uncondensed gas phase and a lower water-layer comprising dissolved oxygenated compounds; combining the last-mentioned lower water-layer with the waterproduct liquid phase for further treatment; and neutralizing the scrubbed gaseous eiiluent to obtain an upper phase comprising acid-free hydrocarbons and a lower phase comprising an aqueous solution of alkali salts.

(II) The steps of I in which the extract obtained from the treatment of the upper oillayer with the aqueous solution of the watersoluble alcohol is hydrogenated to convert aldehydes and ketones present to their corresponding alcohols.

(III) The steps of I and II in which the lower water-layer obtained from water-scrubbing of the oil-product liquid phase is combined with the water-product liquid phase; the combined streams are fractionated to produce a relatively high-boiling fraction comprising a major portion of acids present in the water-product liquid phase; and these acids are subjected to extraction with an oxygen-containing solvent as a water-entrainer to produce substantially waterfree organic acids, upon subsequent solvent recovery.

(IV) The steps of II in which the hydrogenated extract, comprising alcohols, acids and esters is treated with an alkali to convert the acids to their corresponding salts and to saponify esters; the resulting mixture is subjected to reduced pressure to evaporate substantially all of the alcohols from the alkali salts. The alcohols are acidied with an inorganicacid to produce a mixture comprising the corresponding organic acids and inorganic salts; and the organic acids are separated from the inorganic salts.

(V) The steps of IV in which the mixture of organic acids and inorganic salts is separated into an upper acid-rich phase comprising a portion of the acids and water, and a lower waterrich phase comprising the remainder of these acids and inorganic salts; the lower water-rich phase is subjected to extraction with an oxygencontaining solvent as a water-entrainer; to obthe relatively low-boiling fraction is hydrogenated to convert aldehydes and ketones present to their corresponding alcohols and to form a mixture comprising alcohols, organic acids and esters; the mixture thus formed is treated with alkali to convert the organic acids to their corresponding alkali salts and to saponify esters; and alcohols are separated from the alkali salts.

While a particular embodiment of the present invention has been described for purposes of illustration, it should be understood that various modifications and adaptations thereof, which will be obvious to one skilled in the art, may be made within the spirit of the invention as set forth in the appended claims.

Having thus described our invention, we claim:

1. In a process for treating the reaction product obtained in the hydrogenation of oxides of carbon wherein said reaction product is treated to form an oil-product liquid phase and a. waterproduct liquid phase, each of said phases containing oxygenated organic compounds comprising organic acids and alcohols, and wherein said water-product liquid phase is fractionated into a relatively low-boiling fraction comprising alcohols and a relatively high-boiling fraction coml prising organic acids, the improvement which comprises: water-scrubbing said oil-product liquid phase to obtain an aqueous layer comprising water-soluble oxygenated organic compounds and a hydrocarbon layer comprising oil-soluble oxygenated organic compounds; separating said layers; subjecting said hydrocarbon layer to extraction treatment with an aqueous solution of a water-soluble alcohol which is a component of said relatively low-boiling fraction to obtain a rainate phase comprising hydrocarbons and an extract phase comprising oxygenated organic compounds; separating said phases; separating said extract phase into a relatively low-boiling fraction comprising said water-soluble alcohol and oxygenated organic compounds and a relatively high-boiling fraction comprising other oxygenated organic compounds; combining a portion of said last-mentioned relatively low-boiling fraction with said first-mentioned relatively lowboiling fraction obtained from the fractionation of said water-product liquid phase; and separating the streams thus combined into desired components.

2. In a process for treating the reaction product obtained in the hydrogenation of oxides of carbon wherein said reaction product is treated to form an oil-product liquid phase and a waterproduct liquid phase, each of said phases containing oxygenated organic compounds comprising organic acids and alcohols, and wherein said water-product liquid phase is fractionated into a relatively low-boiling fraction comprising alcohols and a relatively high-boiling fraction com- Il prising organic acids. the improvement which comprises: water-scrubbing said oil-product liquid phase to obtain an aqueous layer comprising water-soluble oxygenated organic compounds and a hydrocarbon layer comprising oil-soluble oxygenated organic compounds; separating said layers; subjecting said hydrocarbon layer to extraction treatment with an aqueous solution of a water-soluble alcohol which is a component of said relatively low-boiling fraction to obtain a rafiinate phase comprising hydrocarbons and an extract phase comprising oxygenated organic compounds; separating said phases; separating said extract phase into a relatively low-boiling fraction comprising said water-soluble alcohol and oxygenated organic compounds and a relatively high-boiling fraction comprising other oxygenated organic compounds; combining a portion of said last-mentioned relatively low-boiling fraction with said first-mentioned relatively lowboiling fraction obtained from the fractionation of said water-product liquid phase; separating the streams thus combined into desired componente; and returning the remaining portion of said last-mentioned relatively low-boiling fraction in combination with fresh quantities of said water-soluble alcohol to the extraction treatment of said hydrocarbon layer.

3. In a process for treating the reaction product obtained in the hydrogenation of oxides of carbon wherein said reaction product is treated to form an oil-product liquid phase and a waterproduct liquid phase, each of said phases containing oxygenated organic compounds comprising organic acids and alcohols. and wherein said water-product liquid'phase is fractionated into a relatively low-boiling fraction comprising alcohols and a relatively high-boiling fraction comprising organic acids, the improvement which comprises: treating at least a portion of said oil-product liquid phase with alkali to convert organic acids contained therein to their corresponding alkali salts: writing said alkali salts from said treated portion of said oil-product liquid phase; acidifying said alkali salts with an inorganic acid to produce a mixture comprising the corresponding organic acids and inorganic salts; combining the mixture thus produced with said relatively highboiling fraction; and separating the streams thus combined into desired components.

4. In a process for treating the reaction product obtained in the hydrogenation of oxides of carbon wherein said reaction product is treated to form an oil-product liquid phase and a waterproduct liquid phase, each of said phases containing oxygenated organic compounds comprising organic acids and alcohols, and wherein said water-product liquid phase is fractionated into a relatively low-boiling fraction comprising alcohols and a relatively high-boiling fraction comprising organic acids. and wherein organic acids are separated from said relatively high-boiling fraction, the improvement which comprises: treating at least a portion of said oil-product liquid phase with alkali to convert organic acids contained assen? therein to their corresponding alkali salts; separating said alkali salts from said treated portion of said oil-product liquid phase; acidifying said alkali salts with an inorganic acid to produce a mixture comprising the corresponding organic acids and inorganic salts; separating organic acids from the mixture thus produced; combining organic acids thus separated with organic acids separated from said relatively high-boiling fraction; and separating the streams thus combined into desired components.

5. In a process for treating the reaction product obtained in the hydrogenation of oxides of carbon wherein said reaction product is treated to form an oil-product liquid phase and a waterproduct liquid phase, each of said phases containing oxygenated organic compoundscomprising organic acids and alcohols. and wherein said water-product liquid phase is fractionated into a relatively low-boiling fraction comprising alcohols and organic acids and a relatively highboiling fraction comprising other organic acids. the improvement which comprises: separately treating at least a portion of said relatively lowboiling fraction with alkali to convert organic acids contained therein to their corresponding alkali salts; separating said alkali salts from said treated portion of said relatively low-boiling fraction; acidifying said alkali salts with an inorganic acid to produce a mixture comprising the corresponding organic acids; separately treating at least a portion of said oil-product liquid phase with alkali to convert organic acids contained therein to their corresponding alkali salts: W- rating said alkali salts from said treated portion of said oil-product liquid phase; acidifying said alkali salts with an inorganic acid to produce a mixture comprising the corresponding organic acids and inorganic salts; combining the mixture thus produced with the mixture produced from the treatment of said portion of said relatively low boiling fraction; combining the resulting mixture with said relatively high-boiling fraction; and separating the streams thus combined into desired components.

' WILLIAM P. BURTON.

HENRY G. MCGRATH.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,870,816 Lewis Aug. 9, 1933 2,205,184 Woodhouse June 18, 1940 2,457,257 Michael et al. Dec. 28, 1948 OTHER REFERENCES Fischer: "Conversion of Coal in Oils, pages 242-5, London, Ernest Benn Limited (1925).

U. S. Naval Technical Mission in Europe: The Synthesis of Hydrocarbons and Chemicals From CO and Hz, August 2, 1946, pages 84-92. 

1. IN A PROCESS FOR TREATING THE REACTION PRODUCT OBTAINED IN THE HYDROGENATION OF OXIDES OF CARBON WHEREIN SAID REACTION PRODUCT IS TREATED TO FORM AN OIL-PRODUCT LIQUID PHASE AND A WATERPRODUCT LIQUID PHASE, EACH OF SAID PHASES CONTAINING OXYGENATED ORGANIC COMPOUNDS COMPRISING ORGANIC ACIDS AND ALCOHOLS, AND WHEREIN SAID WATER-PRODUCT LIQUID PHASE IS FRACTIONATED INTO A RELATIVELY LOW-BOILING FRACTION COMPRISING ALCOHOLS AND A RELATIVELY HIGH-BOILING FRACTION COMPRISING ORGANIC ACIDS, THE IMPROVEMENT WHICH COMPRISES: WATER-SCRUBBING SAID OIL-PRODUCT LIQUID PHASE TO OBTAIN AN AQUEOUS LAYER COMPRISING WATER-SOLUBLE OXYGENATED ORGANIC COMPOUNDS AND A HYDROCARBON LAYER COMPRISING OIL-SOLUBLE OXYGENATED ORGANIC COMPOUNDS; SEPARATING SAID LAYERS; SUBJECTING SAID HYDROCARBON LAYER TO EXTRACTION TREATMENT WITH AN AQUEOUS SOLUTION OF A WATER-SOLUBLE ALCOHOL WHICH IS A COMPONENT OF SAID RELATIVELY LOW-BOILING FRACTION TO OBTAIN A RAFFINATE PHASE COMPRISING HYDROCABRONS AND AN EXTRACT PHASE COMPRISING OXYGENATED ORGANIC COMPOUNDS; SEPARATING SAID PHASE; SEPARATING SAID EXTRACT PHASE INTO A RELATIVELY LOW-BOILING FRACTION COMPRISING SAID WATER-SOLUBLE ALCOHOL 